Black dyeing sulphur dyestuffs and process of making same



Patented 1935 I LUNIT ED STATES a 7 Y1 I 2,012,094 M12 BLACK DYEING 'sniirnuiinyns'rnws' AND v 1 'IB SS I HermannBotsand-Ernst DiirgBaseLSWitzerland,.,;' Y

PATENT assignors to Society of Chemical Industry in 1-; f

T iiBasle,'Basel, Switzerland; h 7

l No Drawing Application February 9:1934; Serial v i QNo. 710,570. InSwitzerland Eebriiary 25,1?33 f 5 l 6 Claims. (C etan It is known thatf the leuco indophenol which isivform'ed by reduction of the condensation product from nitrosophenol and "c'arbazole can be converted into dyestuffs containingfsulphur v 18 byltreatment with agents yielding sulphur, differentdyestuffs being obtained according to. the

conditions of the sulphurization.-"If the sulphurizat'ion is' carried out under mild conditions, for

example,'by boiling the leuco-indophenol in .a

10 reflux apparatus with an aqueous sodium polysulphide solution; there are formed-sulphur dyestuffs. By carrying out the sulp hui'ization under more energetic conditions,the formation of the sulphur dyestuff is'repressedbandial vat dyestufi is almost exclusively obtained as a final product. Such processes leading to vat dyestuffs are the processes of Patents-956,3 48, 1,565,736, 1,695,756, and 1,759,261; 2 1 a w I I ;It is further: known that the diarylamines of the general formula wherein R1 represents a naphthalene nucleus and R2 a benzene "nucleus, and wherein further the OH-group stands'in; para-position to the NH-group,- can be converted into 'sulphurized dyestufis by treatment with an agent yielding sulphur Hitherto this treatmentvhas consisted 'either'in melting the diarylaminewith sulphur oli'fin. heating the, diarylamine in an aqueous medu n with s'odiun sulphide or sodium" D013- sulphidel'; The products obtained dye vegetable ffib1ers brown toblue-black, violet-black and black shadesj which, indeed, have aremarkable fastness' to chlorinebut are always weakand. unsightly; H I I V f According to'the present invention dyestufis 40 which are valuable, more particularly on' account oftheir depth ofdyeing'and'lfastness t'o' ,bluefsolutionsl With sodium sulphide and alkalies they-yield leuco compounds of pure yellow colorz-which 'aredistinguished 'by their a great aflinity for the vegetable fiber. :Thus the black dyeings produced] with their aid are 'distin Into-30 parts oi? fused crystallized sodium 'sul-I- phide 'l2 parts of sulphur. are'introduced andthe .mixture" is heated until the sulphuris dissolved; It is then evaporated at about C.-

con-

guished by their surprising coloring power, lfe".

their strength, and further by their good fastness properties to chlorine, washing and light.-

f "As eiiamples of what is m'antby 'sulphurizing under conditions-bywhich-the leuco carbazo1e *5 indophenol is: converted into vat dyestuffs there Lmay be named: the treatment-with"aflpolysul phide'as free'from water as fpossible inpresence of an organic solvent; slich-as alcohol, pyridine;-

p amyl alcohol, cyclohexanol or thelike'if'or-trat 1o.

ment'by the baking processes; such latter pr0c-. t esses' are described in the' p'atents cited in the second paragraphfof" this: specification, particularly valuable resultsbeing obtained with the diarylamines of 'the general f ormula: W 1'5 whe ein the fg'i'bupf linked to thenaphthalene nu llujsiiat the 1- or at the 2-position. The dyestuifsthus ob; tained may be convertedinto the fin shedioxie dized dyestuffs by a suitable oiii'dationf'forin stance by blowing .airthrough the alkaline solution 101' their leuco-cqmpounds, or 1 by action of "the air on the separated dyestuffs, 'orfby any other n'iethodf The following examples illustrate theinven tion without,'- h'oweverylimiting its-"scopef-f-the temperatures, concentrations and proportions of sUJphur'iZing' agen'ts-may be" varied within certain limitsg also the process can be applied to'parent" materials other than those prescribed 40 in theexamples, for instance to 4-hydr'oxydi 'phenylamine or to diarylamines in which both thearyl nuclei belong to: the benzene series. The

process may also be applied to'diarylaniines in which one of 'thearyl nucleifbelong stoafldifier ent series, for instance to the anthracen'e; car- 'bazole or naphthocarbazole series or to the acridine series. The parts? are by weight:

centrated solution is introduced into 7100 artstoi 156 alcohol and there are added 9 parts of l-(4-hydroxy) -phenylaminonaphthalene of the formula,

MPG

and the whole is boiled for 48 hours in a reflux apparatus. The alcohol is then distilled and water is added to take its place. ous solution thus obtained the dyestuff is salted out with common salt or ammonium chloride.

When dry it is a blue-black powder which dyes cotton in a sodium sulphide bath violet-black shades. The dyeings are fast to chlorine.

By substituting 2-(4'-hydroxy)-phenylaminonaphthalene for the 1-(4'-hydroxy) -phenylaminonaphthalene in this example there is produced a-so1newhat more violettish-black dyestuff.

" Ewamplez A concentrated;polysulphide solution is made by dissolving 7 parts of sulphur in 15 parts of crystallized sodium sulphide andevaporating the solution at C. This solution added to 50 parts of cyclohexanol and 3 parts of sulphur and'8 parts of 2;(4-hydroxy),-phenylaminonaphthae lene of'the formula r tuted forthe cyclohexanol.

Example 3 15 parts of crystallized sodium sulphide, 10 parts of water, 18 parts of sulphur, 10 parts of 2-(4 -hydroxy) -phenylaminonaphthalene and 4 parts, of benzidine areintimately mixed and the mixture is dried in a vacuum. It is then baked at'190-200". C. until no more sulphurettedhydrogen evolved. The mass is then treated with hot sodium sulphide solution and filtered, the dyestufi? being precipitated'from the filtrate in the usualmanner. Itproduces on cotton a green- ;ish-black-fast to chlorine; I When 3 parts of carbanilide are substituted for the benzidine in this examaple the product is a reddishblack dyestuff. I V

' Ewam'pZe 4.

Cotton is dyed in the. manner usual for sulphurized dyestuffs with 5 to 6 per cent. of the productofythe'foregoing Example 1, 25 per cent. of. sodium sulphide, 5 grams of calcined sodium 'carbonate: perliter of. vat-liquor and 25 grams ofcalcined sodium sulphate per liter of vat liquor, the ratio fof cotton to liquor being 1:20.

From the aque- The dyestuff is first boiled with the sodium sulphide solution 10 times diluted as well as with the sodium carbonate solution 10 times diluted until it is dissolved. The dyestuif is then added to the vat-liquor, heated to 60 C., the goods are entered and heating is carried nearly to the boiling point. Thereupon Glaubers" salt "is added and the dyeing continued for 1 hour. The yarn is now wrung out and exposed to the air for oxidation. Thorough rinsing and drying conclude the process. I

1 What we claim 'is:--

1. Process for the manufacture of black-dyeing sulphur dyestuffs which are distinguished by their great coloring power, consisting in sulphurizing the diarylamines of the general formula wherein R1 represents an aromatic radical of the naphthalene series and R2 tanvaromatic, radical of the benzene series, wherein-further the OH group stands in 4,-position to theNH-group, with polysulphidesin-the presence of cyclohexanol.

,2. Process. for the manufacture of black-dye ing sulphur dyestuffs which are distinguished by their great coloring power, consisting in sulphurizing the diarylamines of the general formula I wherein the with polysulphidesin the presence of cyclohex anol. I

The black sulphur dyestuffs characterized by theirgreat coloring power, forming black powders which are insoluble-in water and in alcohol, anddissolve in sulphuric acid to pure blue solutions and in dilute sodium sulphide solution to pure yellow solutions, and dyeing cotton in the I manner customary for sulphur dyestuffsdeep blackshades at aratio of dyestuif to material 7 of 5 to 6: 100, which products are obtained by sulphurizing the diarylam'ines of the general formula R1 ll T-R2-OH i n K, H wherein R1 represents an aromatic'radic'alof the naphthalene series and R2 an aromatic radical of the benzene series, wherein further the OH- group stands in 4-position to the NI-I-group.

5; The black sulphur'dyestuifs characterized 1 by their great coloring power, forming black powders which are insoluble in water and in alcohol, and dissolve in sulphuric acid to pure blue solutions andin dilute sodium sulphide solution to pure yellow solutions, and dyeing cotton in the T5 manner customa y 10 whefein the 1- or at the 2-pos1t1on.

} its great coloring power, forming a black powder for sulphur dyestuffs deep black shades at a ratio of dyestuff to material of 5 to 6:100, which productsare obtained by sul- Vphurizing the diarylamines of the general formula roup is linked to the naphthalene nucleus at the e. The black sulphur dyestuif characterized by manner customary for sulphur dyestuffs deep black shades at a ratio of dyestufi to material of 5 to 6:100, which product is obtained by sulphurizing the diarylamine of the formula HERMANN'BoTs.

ERNST Dim. 

